CN103709201B - A kind of preparation method of rhodium dicarbonyl acetylacetonate and the method for olefin hydroformylation - Google Patents
A kind of preparation method of rhodium dicarbonyl acetylacetonate and the method for olefin hydroformylation Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of rhodium dicarbonyl acetylacetonate, it is characterized in that, the method comprises: the Trichlororhodium aqueous solution, under the condition of precipitin reaction, contacts with precipitation agent by (1), to make rhodium element precipitate, obtains the precipitation containing rhodium element; (2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm; (3) under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, contact with methyl ethyl diketone after the described resolution of precipitate containing rhodium element that step (2) is obtained.The invention also discloses a kind of method of olefin hydroformylation.The present invention can realize reducing product chloride ion content, improves product synthesis yield, improves the goal of the invention of rhodium dicarbonyl acetylacetonate catalytic activity.
Description
Technical field
The present invention relates to a kind of preparation method of rhodium dicarbonyl acetylacetonate and the method for olefin hydroformylation; being specifically related to a kind of employing Trichlororhodium hydrate is raw material; by forming the method preparing rhodium dicarbonyl acetylacetonate containing the precipitation of rhodium element again, and include the method that the alkene of preparation method of rhodium dicarbonyl acetylacetonate and synthetic gas carry out hydroformylation reaction.
Background technology
Rhodium dicarbonyl acetylacetonate (Rh (CO)
2(acac)) be alpha-olefin and synthetic gas (CO and H
2mixed gas) occur that hydroformylation reaction is just generating, the good catalyst precursor of isomery aldehyde.Such as, propylene and synthetic gas are at Rh (CO)
2(acac) there is lower generation butyraldehyde-n and isobutyric aldehyde in homogeneous catalyst precursor.
" preparing the simple method of rhodium dicarbonyl acetylacetonate (I) " (Russian Chinese Journal of Inorganic Chemistry, Wa Shaweisi is based on sand etc., 1967,12 (6), 1709) (Simplemethodofpreparingacetylacetonatedicarbonylrhodium (I), VarshavskiiYu.S., ZhurnalNeorganicheskoiKhimii, 1967,12 (6), 1709) refer to Trichlororhodium hydrate (RhCl in
3xH
2o) be raw material one-step synthesis Rh (CO)
2(acac).By RhCl
3xH
2o joins in dimethyl formamide (DMF) as starting raw material and dissolves, and is heated to 150 DEG C, treats RhCl
3xH
2add methyl ethyl diketone again after O all dissolves, reflux 1 hour, after cooling, add the deionized water of more than several times, Rh (CO)
2(acac) flocks that takes on a red color is separated out.Red and green color needle crystal is obtained with hexane recrystallization, Rh (CO) after filtering
2(acac) yield is 75%.
" dicarbapentaborane-beta-diketon of rhodium (I) and related compound " (the Fu Bona base of a fruit and outstanding Wilkinson, Chemical Society's proceedings, 1964,3156-3160) (Dicarbonyl-β-diketonato-andRelatedComplexesofRhodium (I), F.BonatiandG.Wilkinson, J.Chem.Soc., 1964,3156-3160) in refer to RhCl
3xH
2o is raw material two step synthesis Rh (CO)
2(acac).At 100 DEG C, toward the RhCl of porphyrize
3xH
2pass into carbon monoxide in O, obtain [Rh (CO)
2cl]
2, then with [Rh (CO)
2cl]
2for raw material, sherwood oil are solvent, add methyl ethyl diketone and barium carbonate refluxes 1 week at 100 DEG C.Red and green color needle-like Rh (CO) is obtained through concentrating under reduced pressure
2(acac) crystallization.Two steps synthesis Rh (CO)
2(acac) total recovery is 85%.
CN102030781A discloses a kind of preparation method of rhodium dicarbonyl acetylacetonate, it is characterized in that: comprise in 60-120 DEG C of alcoholic solution carbon monoxide being passed into water and rhodium chloride and react 60-120 minute, add a certain amount of acetylacetonate and continue reaction 60-90 minute, Separation and Recovery product; Described alcohol is selected from one or more in methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol; The concentration of the alcoholic solution of described water and rhodium chloride is 0.10-1.00 mol/L; The add-on of described acetylacetonate is the mol ratio of methyl ethyl diketone ion and the rhodium making to contain in acetylacetonate is 3.0-8.0; Described acetylacetonate be selected from methyl ethyl diketone lithium, methyl ethyl diketone sodium, methyl ethyl diketone potassium, magnesium acetylacetonate, aluminium acetylacetonate one or more.Obtain green solid by the method for this disclosure of the invention, yield is 93.9 % by weight.FTIR spectrum (FTIR) shows that carbon monoxide, methyl ethyl diketone and rhodium define coordination.But from patent specification content, this green solid, without fusing point test, ultimate analysis, nuclear magnetic resonance spectroscopy, cannot confirm that this solid must be Rh (CO)
2(acac).
Existing method obtains Rh (CO)
2(acac) yield is not high, and rhodium is the precious metal that a kind of price is extremely expensive, realizes batch production Rh (CO)
2(acac) gordian technique improves synthesis yield, to reduce rhodium loss.In addition, Rh (CO)
2(acac), when being used as catalyzer in propylene and synthetic gas generation hydroformylation reaction, find that the catalytic activity of catalyzer in the lower or reaction process of the catalytic activity of catalyzer declines clearly.Therefore, Rh (CO) is solved
2(acac) catalytic activity and raising Rh (CO)
2(acac) yield problem is the important problem that propylene and synthetic gas carry out hydroformylation reaction and face.
Summary of the invention
The object of the invention is the problem overcoming existing rhodium dicarbonyl acetylacetonate poor catalytic activity and improve rhodium dicarbonyl acetylacetonate yield; there is provided a kind of catalytic activity of preparing high and prepare the method for the high rhodium dicarbonyl acetylacetonate of yield, a kind of method of the olefin hydroformylation containing this rhodium dicarbonyl acetylacetonate preparation method is provided in addition.
The present inventor is found by research; existing rhodium dicarbonyl acetylacetonate catalytic activity is low or catalytic activity reduction is obvious; because the content of wherein impurity chlorine ion is higher; often be greater than 0.1 % by weight; and chlorion is the toxicant of catalyzer in hydroformylation reaction, even if the chlorion (in cl content in reaction solution) carrying out bringing into hydroformylation reaction system 1ppm to propylene and synthetic gas from rhodium dicarbonyl acetylacetonate itself or other raw material also can make rhodium catalyst poisoning rapidly.For this reason, the chloride ion content as far as possible reduced in rhodium dicarbonyl acetylacetonate is needed.
Although prior art is by synthesizing the mode of acetylacetonatodicarrhodium rhodium more further by rhodium dicarbonyl acetylacetonate, the chloride ion content in rhodium dicarbonyl acetylacetonate can be reduced, but so not only increase the complexity of preparation, and reduce the synthesis yield of rhodium-containing product.Rhodium is also the precious metal that a kind of price is extremely expensive, and therefore higher yield is the key point realizing rhodium dicarbonyl acetylacetonate batch production.
To this, the present inventor is by studying discovery further, in the process of rhodium dicarbonyl acetylacetonate preparation method, first Trichlororhodium is prepared into precipitation containing rhodium element through precipitin reaction, chloride ions displace is got off, and by further filtering, washing reduces the content of chlorion in the precipitation containing rhodium element, carry out the reaction of synthesis of acetyl acetone dicarbonyl rhodium again, can ensure like this in the process of follow-up synthesis of acetyl acetone dicarbonyl rhodium, less introducing chlorion in product, therefore the chloride ion content of rhodium dicarbonyl acetylacetonate product not only can be made qualified, and decrease in prior art and need further synthesis to be processed into the preparation process of acetylacetonatodicarrhodium rhodium, improve the synthesis yield obtaining rhodium dicarbonyl acetylacetonate product.Complete the present invention thus.
To achieve these goals, the invention provides a kind of preparation method of rhodium dicarbonyl acetylacetonate, it is characterized in that, the method comprises:
(1) under the condition of precipitin reaction, the Trichlororhodium aqueous solution is contacted with precipitation agent, to make rhodium element precipitate, obtain the precipitation containing rhodium element;
(2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm;
(3) under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, contact with methyl ethyl diketone after the described resolution of precipitate containing rhodium element that step (2) is obtained.
The present invention also provides a kind of method of olefin hydroformylation; the method comprises prepares rhodium dicarbonyl acetylacetonate; and obtained described rhodium dicarbonyl acetylacetonate is used for the hydroformylation reaction of alkene and synthetic gas; it is characterized in that, the method preparing rhodium dicarbonyl acetylacetonate is the preparation method of above-mentioned rhodium dicarbonyl acetylacetonate.
By technique scheme provided by the invention; the content of the chlorion in the rhodium dicarbonyl acetylacetonate product prepared is less than 100ppm; the total recovery of synthesis of acetyl acetone dicarbonyl rhodium is greater than 95%, and the rhodium dicarbonyl acetylacetonate obtained directly can be used as the catalyst precursor of propylene and synthetic gas generation hydroformylation reaction generation butyraldehyde-n and isobutyric aldehyde.Such as, in embodiment 3, after Trichlororhodium being precipitated as rhodium hydroxide precipitation, carry out the reaction of synthesis of acetyl acetone dicarbonyl rhodium again, the chloride ion content in the rhodium dicarbonyl acetylacetonate product obtained only has 38ppm, and in rhodium, synthesis yield reaches 97.9%.In embodiment 6-8, directly use rhodium dicarbonyl acetylacetonate to carry out the hydroformylation reaction of propylene and synthetic gas as catalyst precursor, the speed of reaction of mensuration is 0.78mol/hL, active identical under identical rhodium concentration condition with the catalyzer that full scale plant uses.And the rhodium dicarbonyl acetylacetonate using prior art to prepare in comparative example 1, in the product obtained, chloride ion content reaches 3200ppm, and in rhodium, yield also only has 88.4%; And the speed of carrying out catalyzing propone hydroformylation reaction is 0.66mol/hL, only have 85% of full scale plant used catalyst activity.Therefore, technical scheme provided by the invention can solve that detrimental impurity chloride ion content is high, synthesis of acetyl acetone dicarbonyl rhodium yield is low and the problem of rhodium dicarbonyl acetylacetonate poor catalytic activity effectively, realizes goal of the invention of the present invention.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of rhodium dicarbonyl acetylacetonate, it is characterized in that, the method comprises:
(1) under the condition of precipitin reaction, the Trichlororhodium aqueous solution is contacted with precipitation agent, to make rhodium element precipitate, obtain the precipitation containing rhodium element;
(2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm;
(3) under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, contact with methyl ethyl diketone after the described resolution of precipitate containing rhodium element that step (2) is obtained.
According to the present invention, in the preparation method of described rhodium dicarbonyl acetylacetonate, step (1) is for by Trichlororhodium hydrate deposition being the precipitation containing containing rhodium element, can comprise and first make the Trichlororhodium aqueous solution by Trichlororhodium hydrate dissolution to water, then under precipitin reaction condition, in the Trichlororhodium aqueous solution, add precipitation agent and carry out precipitin reaction, obtain the precipitation containing rhodium element, control the temperature of precipitin reaction, control the pH value that precipitin reaction obtains the reaction mixture of the precipitation containing rhodium element, to ensure that the rhodium in the Trichlororhodium aqueous solution precipitates completely, obtain the reaction mixture containing the precipitation containing rhodium element.
According to the present invention, the described precipitation agent used can be any can by precipitation agent that rhodium is precipitated out with the form that rhodium precipitates from Trichlororhodium hydrate, under preferable case, described precipitation agent is the aqueous solution of ammoniacal liquor and/or alkali metal hydroxide, one or more in preferred NaOH, KOH and ammoniacal liquor.In the preferred case, described rhodium is precipitated as yellow rhodium hydroxide precipitation.
According to the present invention, the described precipitation agent of use can use in the form of a solution, and the concentration of precipitant solution can be selected in relative broad range, and under preferable case, described precipitation agent is that the solution form of 0.1-5mol/L uses with volumetric molar concentration; Preferred described precipitation agent is that the solution form of 1-3mol/L uses with volumetric molar concentration.Wherein, when described precipitation agent is ammoniacal liquor, described precipitation agent is that the solution form of 1-3mol/L uses and refers to that the ammoniacal liquor that uses volumetric molar concentration to be 1-3mol/L is as precipitation agent with volumetric molar concentration.In the present invention, the concentration of ammoniacal liquor continues to use the common implication in this area.
According to the present invention, when Trichlororhodium hydrate dissolution and water form the described Trichlororhodium aqueous solution, under preferable case, in the described Trichlororhodium aqueous solution, the volumetric molar concentration of rhodium is 0.1-5mol/L; In the preferred described Trichlororhodium aqueous solution, the volumetric molar concentration of rhodium is 1-3mol/L.
According to the present invention, the condition of described precipitin reaction is complete with the precipitation that can be conducive to containing rhodium element, and the loss of rhodium can be reduced, under preferable case, the condition of described precipitin reaction comprises: precipitation temperature is 5-10 DEG C, the consumption of precipitation agent makes the pH value after precipitin reaction between 7-10, and preferable ph is between 7-8.
According to the present invention, under precipitin reaction condition, in the Trichlororhodium aqueous solution, add precipitation agent carry out precipitin reaction, described in add and can carry out by any way, under preferable case, described in be incorporated as dropping.
According to the present invention, in the preparation method of described rhodium dicarbonyl acetylacetonate, step (2) is described containing the chlorion in the precipitation of rhodium element for reducing further on the basis of precipitin reaction, can comprise and first the reaction mixture containing the precipitation containing rhodium element be carried out solid-liquid separation, isolate the precipitation containing rhodium element, then washing and filtering obtain containing the precipitation of rhodium element, control wash temperature, control medium and the number of times of washing use, to make the content containing chlorion in the precipitation of rhodium element after washing lower than 1000ppm, preferably lower than 500ppm.In the present invention, ppm refers to quality hundred content very much.
In the present invention, the content of chlorion in the precipitation that can detect containing rhodium element by inductivity coupled plasma mass spectrometry (ICP-MS) mode.The precipitation containing rhodium element after washing preferably carries out vacuum-drying in order to follow-up use at 25 DEG C.
According to the present invention, described washing can use conventional washing methods, controls wash conditions to realize better washing effect and to make rhodium lose few, under preferable case, make successively to wash with water 2-5 time, hexanaphthene washs 1 time, wash temperature is 5-10 DEG C.
According to the present invention, the described solid-liquid separation of being carried out by the reaction mixture containing the precipitation containing rhodium element can be any method, and under preferable case, described solid-liquid separation is filtration under diminished pressure.
According to the present invention, in the preparation method of described rhodium dicarbonyl acetylacetonate, step (3) is for the building-up reactions of rhodium dicarbonyl acetylacetonate, can comprise and first add organic solvent containing the precipitation of rhodium element dissolve what washed, obtain the mixture containing the precipitation containing rhodium element, by the solution of the precipitation containing rhodium element is heated to more than 140 DEG C, the solution boiling containing the precipitation containing rhodium element can be kept, the precipitation containing rhodium element all dissolved; Then, under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, slowly add methyl ethyl diketone under reflux state and carry out building-up reactions in the solution containing the precipitation containing rhodium element.After adding methyl ethyl diketone, continue to keep the reaction of synthesis of acetyl acetone dicarbonyl rhodium at boiling, reflux state, control reaction times and temperature of reaction, obtain the reaction solution containing rhodium dicarbonyl acetylacetonate.Stop building-up reactions, carry out aftertreatment, first the reaction solution of cooling containing rhodium dicarbonyl acetylacetonate, then the chilled reaction solution containing rhodium dicarbonyl acetylacetonate is poured in deionized water, produce the precipitation of red cotton-shaped rhodium dicarbonyl acetylacetonate, then filter the precipitation of rhodium dicarbonyl acetylacetonate, the organic solvent of the precipitation containing rhodium element is dissolved in removing, obtains the crude product of rhodium dicarbonyl acetylacetonate.Then the crude product of rhodium dicarbonyl acetylacetonate is carried out recrystallization, washing, drying obtain rhodium dicarbonyl acetylacetonate finished product.
According to the present invention, after described precipitin reaction, with the reaction carrying out synthesis of acetyl acetone dicarbonyl rhodium described in obtaining containing the precipitation of rhodium element as starting raw material.The condition of described building-up reactions can be the condition known to those skilled in the art.
According to the present invention, the described precipitation containing rhodium element is joined in organic solvent and dissolves, obtain the solution containing the precipitation containing rhodium element, under preferable case, the organic solvent dissolving the described precipitation containing rhodium element is dimethylformamide, relative to the rhodium element of 1 mole, the consumption of dimethylformamide is 1-3L; The consumption of preferred dimethylformamide is 1.5-2L.Described dimethylformamide can be DMF and/or N,N-dimethylacetamide, is preferably DMF.
According to the present invention, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium, described rhodium dicarbonyl acetylacetonate can be obtained, under preferable case, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium comprises: the mol ratio of described methyl ethyl diketone and rhodium is 8-15:1, temperature of reaction is 140-160 DEG C, and the reaction times is 50-90 minute; The mol ratio of preferred described methyl ethyl diketone and rhodium is 9-12:1, and temperature of reaction is 150 DEG C.
According to the present invention, after the reaction completing described synthesis of acetyl acetone dicarbonyl rhodium, the reaction solution containing rhodium dicarbonyl acetylacetonate described in being obtained by reacting is carried out aftertreatment.First be cooled to 5-10 DEG C, then import the red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation of generation in 5-10 DEG C of water, described water is preferably deionized water.Then by filtering the described organic solvent removed containing the precipitation of rhodium element described in above-mentioned dissolving, the crude product of described rhodium dicarbonyl acetylacetonate is obtained.
According to the present invention, in order to remove the impurity of rhodium dicarbonyl acetylacetonate precipitation surface further, under preferable case, described method also comprises carries out recrystallization by the crude product of the rhodium dicarbonyl acetylacetonate obtained, and obtains the rhodium dicarbonyl acetylacetonate crystal finished product in red and green color.Described recrystallization is recrystallization method known in those skilled in the art, and under preferable case, the solvent of use is normal hexane or hexanaphthene, and recrystallization number of times is 1 time.Carry out afterwards washing and drying, obtain the finished product of rhodium dicarbonyl acetylacetonate.The solvent that described washing uses is the organic solvent not dissolving described rhodium dicarbonyl acetylacetonate precipitation, and under preferable case, described organic solvent is normal hexane or hexanaphthene.
According to the present invention, in the reaction carrying out described synthesis of acetyl acetone dicarbonyl rhodium, rare gas element can be used to prevent the rhodium in described rhodium dicarbonyl acetylacetonate and the oxygen generation oxidizing reaction in air, under preferable case, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium also comprises carries out in a nitrogen atmosphere.
According to the present invention, by the preparation method of described rhodium dicarbonyl acetylacetonate, the chloride ion content in the described rhodium dicarbonyl acetylacetonate obtained is lower than 100ppm.
The present invention also provides a kind of olefin hydroformylation method; the method comprises prepares rhodium dicarbonyl acetylacetonate; and obtained described rhodium dicarbonyl acetylacetonate is used for the hydroformylation reaction of alkene and synthetic gas; it is characterized in that, the method preparing rhodium dicarbonyl acetylacetonate is the preparation method of described rhodium dicarbonyl acetylacetonate.
According to the present invention, the method preparing rhodium dicarbonyl acetylacetonate is the preparation method of described rhodium dicarbonyl acetylacetonate described above, does not repeat them here.
According to the present invention, the method for described hydroformylation of olefin and condition are content known in those skilled in the art, can be any can realize this reaction method and corresponding condition.In the present invention, described hydroformylation of olefin adopts rhythmic reaction method, and the method comprises: rhodium dicarbonyl acetylacetonate, part and organic solvent are put into autoclave by a certain amount of by (1); (2) under certain temperature, pressure condition, by raw material olefin, H
2continue by a certain percentage to pass in autoclave to react with CO.
By under certain catalyst solution concentration (in rhodium element), the mole number that in the unit time, in per volume of catalyst solution, reaction mass (in alkene) consumes calculates the rate of catalysis reaction of hydroformylation of olefin.The rate of catalysis reaction obtained is the initial reaction rate of the hydroformylation of olefin under this catalyst solution concentration.
Described part is can form the P contained compound of rhodium-phosphine complex with rhodium dicarbonyl acetylacetonate, and can be single phosphine or biphosphine ligand, part can have one or more identical or different substituted radical, and under preferable case, described part is triphenylphosphine.
Described organic solvent is to dissolve the butyraldehyde-n and isobutyric aldehyde that described propene hydroformylation reaction obtains, and can be one or more in benzene, toluene and trimerization butyraldehyde, be preferably trimerization butyraldehyde.
Described alkene can be the alkene of various routine, such as, can be the alkene of C2-C8.Most preferably, described alkene is propylene.
It is 100 DEG C that described reaction conditions comprises temperature, and pressure is 0.55MPa.The ratio that described raw material passes into is propylene: H
2: CO=1:1:1(mol ratio).In the present invention, described pressure refers to absolute pressure.
According to the present invention, the method for described olefin hydroformylation is the hydroformylation reaction of alkene and synthetic gas, and under preferable case, described hydroformylation of olefin is the reaction that propylene and synthetic gas generation hydroformylation reaction generate butyraldehyde-n and isobutyric aldehyde.
Precipitin reaction is passed through in the present invention, rhodium in the Trichlororhodium aqueous solution is transformed into the precipitation containing rhodium element, make in the chemical constitution of the building-up reactions raw material preparing rhodium dicarbonyl acetylacetonate not containing chlorine element, further washing step can remove chlorion residual in precipitation, thus reduces the content of chlorion in the finished product rhodium dicarbonyl acetylacetonate.Owing to decreasing preparation process rhodium dicarbonyl acetylacetonate synthesis being changed into acetylacetonatodicarrhodium rhodium in the present invention, not only improve the synthesis yield of rhodium dicarbonyl acetylacetonate, and the rhodium dicarbonyl acetylacetonate obtained can be directly used in required building-up reactions, and rhodium dicarbonyl acetylacetonate synthesis must be changed into acetylacetonatodicarrhodium rhodium ability industrial application by prior art.
Below will be described the present invention by embodiment, but the present invention is not limited thereto.
In following examples, chlorine ions content uses the 7500CX icp ms (ICP-MS) of Agilent company to analyze.
The finished product prepared are measured by Fourier transformation infrared spectrometer, contrast, determine that the product prepared is rhodium dicarbonyl acetylacetonate with the standard spectrogram (AldrichAlcoholsandPhenols composes storehouse) of rhodium dicarbonyl acetylacetonate.Infrared spectroscopy adopts THERMOFISHERSCIENTIFIC company NICOLETNEXUS470FT-IR instrument, adopts KBr pressed disc method to measure.
The content of rhodium in analysed preparation rhodium dicarbonyl acetylacetonate, adopts the AAnalyst400 type Atomic Absorption Spectroscopy AAS purchased from Perkinelmer Inc. to analyze.In the catalyzer used in hydroformylation of olefin rhodium element quality (g)=rhodium dicarbonyl acetylacetonate in content (quality the %) × rhodium dicarbonyl acetylacetonate of rhodium add quality (g).
The synthesis yield of rhodium dicarbonyl acetylacetonate product, in rhodium element, calculates according to the following formula:
The raw material used in following examples and comparative example is all available commercially.
Embodiment 1
The present embodiment is for illustration of the preparation method of rhodium dicarbonyl acetylacetonate provided by the invention.
(1) precipitin reaction: in 1500ml beaker, add the Trichlororhodium aqueous solution that 250.0mlRh concentration is 1.000mol/L, under magnetic stirring, controlling temperature of reaction is 10 DEG C, dropping concentration is that the NaOH solution of 1.00mol/L is about 750ml, the change of monitoring solution ph, stops when solution ph=8.0 dripping.Obtain the reaction soln containing rhodium hydroxide precipitation.
(2) washing precipitation: by the reaction soln filtration under diminished pressure precipitated containing rhodium hydroxide, isolates rhodium hydroxide precipitation.With the deionized water wash three times that temperature is 10 DEG C, finally wash one time with 10 DEG C of hexanaphthenes.25 DEG C of vacuum-dryings, obtain yellow rhodium hydroxide precipitation.The content measuring chlorion in rhodium hydroxide precipitation is 495ppm.
(3) synthesis of acetyl acetone dicarbonyl rhodium: first the rhodium hydroxide of gained precipitation is put into three mouthfuls of reaction flasks that 1000ml is provided with reflux exchanger.Add 375ml analytical pure DMF; Stir; Be heated to 150 DEG C, boiling; Under total reflux state, treat that rhodium hydroxide precipitation is dissolved completely, obtain the solution containing rhodium hydroxide precipitation, solvent is DMF, and in solution, the volumetric molar concentration of rhodium is 0.666mol/L.
Then the reaction of synthesis of acetyl acetone dicarbonyl rhodium is carried out.In the solution precipitated containing rhodium hydroxide, slowly add 225 grams of analytical pure methyl ethyl diketones, the mol ratio of methyl ethyl diketone and rhodium is 9:1.Control reaction heating 150 DEG C, reflux and pass into nitrogen protection react 50 minutes after stopping.Obtain the reaction solution containing rhodium dicarbonyl acetylacetonate.
After cooling reaction solution to 10 DEG C, being poured into and filling 3100ml temperature is in the beaker of 10 DEG C of deionized waters, generates red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation.Cross and filter DMF solvent, obtain rhodium dicarbonyl acetylacetonate crude product.By the rhodium dicarbonyl acetylacetonate crude product prepared, with normal hexane recrystallization, washing, vacuum-drying at 25 DEG C, namely obtain the crystal the finished product 61.5 grams in red and green color.Fourier infrared spectrograph is measured the spectrogram that the finished product obtain, contrast with the standard spectrogram of rhodium dicarbonyl acetylacetonate, determine that crystal the finished product are rhodium dicarbonyl acetylacetonate.
Product analysis the results are shown in Table 1.
Embodiment 2
The present embodiment is for illustration of the preparation method of rhodium dicarbonyl acetylacetonate provided by the invention.
(1) precipitin reaction: in 1000ml beaker, adds the Trichlororhodium aqueous solution that 150.0mlRh concentration is 2.000mol/L.Under magnetic stirring, controlling temperature of reaction is 7 DEG C, and dropping concentration is that the KOH solution of 3.00mol/L is about 300ml, and the change of monitoring solution ph stops when solution ph=7.0 dripping.Obtain the reaction soln containing rhodium hydroxide precipitation.
(2) washing precipitation: by the reaction soln filtration under diminished pressure precipitated containing rhodium hydroxide, isolates rhodium hydroxide precipitation.With the deionized water wash three times that temperature is 8 DEG C, finally wash one time with 7 DEG C of hexanaphthenes.25 DEG C of vacuum-dryings, obtain yellow rhodium hydroxide precipitation.The content measuring chlorion in rhodium hydroxide precipitation is 450ppm.
(3) synthesis of acetyl acetone dicarbonyl rhodium: first the rhodium hydroxide of gained precipitation is put into three mouthfuls of reaction flasks that 1500ml is provided with reflux exchanger.Add 600ml analytical pure DMF, stir, be heated to 150 DEG C, boiling; Under total reflux state, treat that rhodium hydroxide precipitation is dissolved completely, obtain the solution containing rhodium hydroxide precipitation, solvent is DMF, and in solution, the volumetric molar concentration of rhodium is 0.50mol/L.
Then the reaction of synthesis of acetyl acetone dicarbonyl rhodium is carried out.In the solution precipitated containing rhodium hydroxide, slowly add 360 grams of analytical pure methyl ethyl diketones, the mol ratio of methyl ethyl diketone and rhodium is 12:1.Control reaction heating 150 DEG C, backflow, reaction 90 minutes after stop.Obtain the reaction solution containing rhodium dicarbonyl acetylacetonate.
After cooling reaction solution to 7 DEG C, being poured into and filling 5800ml temperature is in the beaker of 7 DEG C of deionized waters, generates red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation.Cross and filter DMF solvent, obtain rhodium dicarbonyl acetylacetonate crude product.By the rhodium dicarbonyl acetylacetonate crude product prepared, with hexanaphthene recrystallization, washing, vacuum-drying at 25 DEG C, namely obtain the crystal the finished product 75.1 grams in red and green color.Determine that crystal the finished product are rhodium dicarbonyl acetylacetonate.
Product analysis the results are shown in Table 1.
Embodiment 3
The present embodiment is for illustration of the preparation method of rhodium dicarbonyl acetylacetonate provided by the invention.
(1) precipitin reaction: in 1000ml tri-mouthfuls of reaction flasks, adds the Trichlororhodium aqueous solution that 80.0mlRh concentration is 2.500mol/L.Under magnetic stirring, controlling temperature of reaction is 5 DEG C, and dropping concentration is that the ammonia soln of 2.00mol/L is about 300ml, and the change of monitoring solution ph stops when solution ph=7.5 dripping.Obtain the reaction soln containing rhodium hydroxide precipitation.
(2) washing precipitation: by the reaction soln filtration under diminished pressure precipitated containing rhodium hydroxide, isolates rhodium hydroxide precipitation.With the deionized water wash three times that temperature is 5 DEG C, finally wash one time with 5 DEG C of hexanaphthenes.25 DEG C of vacuum-dryings.Obtain yellow rhodium hydroxide precipitation.The content measuring chlorion in rhodium hydroxide precipitation is 410ppm.
(3) synthesis of acetyl acetone dicarbonyl rhodium: first the rhodium hydroxide of gained precipitation is put into three mouthfuls of reaction flasks that 1000ml is provided with reflux exchanger.Add 360ml analytical pure DMF, stir, be heated to 150 DEG C, boiling; Under total reflux state, treat that rhodium hydroxide precipitation is dissolved completely, obtain the solution containing rhodium hydroxide precipitation, solvent is DMF, and in solution, the volumetric molar concentration of rhodium is 0.55mol/L.
Then the reaction of synthesis of acetyl acetone dicarbonyl rhodium is carried out.In the solution precipitated containing rhodium hydroxide, slowly add 210 grams of analytical pure methyl ethyl diketones, the mol ratio of methyl ethyl diketone and rhodium is 10.5:1.Control reaction heating 150 DEG C, backflow, reaction 80 minutes after stop.Obtain the reaction solution containing rhodium dicarbonyl acetylacetonate.
After cooling reaction solution to 5 DEG C, being poured into and filling 5800ml temperature is in the beaker of 5 DEG C of deionized waters, generates red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation.Cross and filter DMF solvent, obtain rhodium dicarbonyl acetylacetonate crude product.By the rhodium dicarbonyl acetylacetonate crude product prepared, with hexanaphthene recrystallization, washing, vacuum-drying at 25 DEG C, namely obtain the crystal the finished product 50.6 grams in red and green color.Determine that crystal the finished product are rhodium dicarbonyl acetylacetonate.
Product analysis the results are shown in Table 1.
Embodiment 4
The present embodiment is for illustration of the preparation method of rhodium dicarbonyl acetylacetonate provided by the invention.
According to the method for embodiment 3, unlike, in precipitin reaction, the change of monitoring solution ph, when solution ph=10 stop dripping, obtains the reaction soln containing rhodium hydroxide.
Product analysis the results are shown in Table 1.
Embodiment 5
According to the method for embodiment 3, continue synthesis of acetyl acetone triphenylphosphine rhodium carbonyl.
Synthesis of acetyl acetone triphenylphosphine rhodium carbonyl: rhodium dicarbonyl acetylacetonate crystal 50.6g is added the heating of 0.566L benzene, stir, be warming up to 80 DEG C, make it dissolve completely, obtain the solution containing rhodium dicarbonyl acetylacetonate, wherein the volumetric molar concentration of rhodium dicarbonyl acetylacetonate is 0.35mol/L.Simultaneously by 83g triphenylphosphine dissolved in 422ml benzene, obtain the organic solvent containing triphenylphosphine, wherein the volumetric molar concentration of triphenylphosphine is 0.75mol/L.
Then the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is carried out.Under agitation, isothermal reaction at 75 DEG C, drip containing in the solution of rhodium dicarbonyl acetylacetonate the benzole soln 422ml that above-mentioned triphenylphosphine concentration is 0.75mol/L to obtained above, wherein the mol ratio of rhodium dicarbonyl acetylacetonate and triphenylphosphine is 1:1.6, carry out building-up reactions, and have CO bubble to produce.After question response does not have CO bubble to produce, stopped reaction, obtains the reaction solution containing acetylacetonatodicarrhodium rhodium.
Reaction solution is cooled to 5 DEG C, separates out yellow crystals.Filtration obtains yellow crystals, washs 3 times with the benzole solns of 5 DEG C, then 25 DEG C of vacuum-dryings, obtains finished product 96.55 grams.Determine that finished product is acetylacetonatodicarrhodium rhodium.
The finished product prepared is measured by Fourier transformation infrared spectrometer, contrast with the standard spectrogram (AldrichAlcoholsandPhenols composes storehouse) of acetylacetonatodicarrhodium rhodium, determine that the product prepared is acetylacetonatodicarrhodium rhodium.Infrared spectroscopy adopts THERMOFISHERSCIENTIFIC company NICOLETNEXUS470FT-IR instrument, adopts KBr pressed disc method to measure.
The content of rhodium in analysed preparation acetylacetonatodicarrhodium rhodium, adopts the AAnalyst400 type Atomic Absorption Spectroscopy AAS purchased from Perkinelmer Inc. to analyze.In the catalyzer used in hydroformylation of olefin rhodium element quality (g)=acetylacetonatodicarrhodium rhodium in content (quality the %) × acetylacetonatodicarrhodium rhodium of rhodium add quality (g).
The synthesis yield of acetylacetonatodicarrhodium rhodium product, in rhodium element, calculates according to the following formula:
Product analysis the results are shown in Table 1.
Comparative example 1
According to the method for embodiment 3, unlike, there is no precipitin reaction step and washing precipitation step.In synthesis of acetyl acetone dicarbonyl rhodium step, the Trichlororhodium aqueous solution being 2.500mol/L with 80mlRh concentration substitutes rhodium hydroxide precipitation; Simultaneously after obtaining rhodium dicarbonyl acetylacetonate crude product, carry out recrystallization secondary with normal hexane.Measure the chloride ion content of the rhodium dicarbonyl acetylacetonate of synthesis, analytical results is in table 1.
Comparative example 2
According to the method for embodiment 3, unlike: there is no precipitin reaction step and washing precipitation step; After obtaining rhodium dicarbonyl acetylacetonate, then be prepared into acetylacetonatodicarrhodium rhodium through synthesis acetylacetonatodicarrhodium rhodium step.
In synthesis of acetyl acetone dicarbonyl rhodium step, the Trichlororhodium aqueous solution being 2.500mol/L with 80mlRh concentration substitutes rhodium hydroxide precipitation.The rhodium dicarbonyl acetylacetonate crude product obtained, carries out recrystallization secondary with normal hexane.
Synthesis of acetyl acetone triphenylphosphine rhodium carbonyl: rhodium dicarbonyl acetylacetonate crystal 46.65g is added the heating of 0.566L benzene, stir, be warming up to 80 DEG C, make it dissolve completely, obtain the solution containing rhodium dicarbonyl acetylacetonate, wherein the volumetric molar concentration of rhodium dicarbonyl acetylacetonate is 0.32mol/L.Simultaneously by 83g triphenylphosphine dissolved in 422ml benzene, obtain the organic solvent containing triphenylphosphine, wherein the volumetric molar concentration of triphenylphosphine is 0.75mol/L.
Then the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is carried out.Under agitation, isothermal reaction at 75 DEG C, drip containing in the solution of rhodium dicarbonyl acetylacetonate the benzole soln 422ml that above-mentioned triphenylphosphine concentration is 0.75mol/L to obtained above, wherein the mol ratio of rhodium dicarbonyl acetylacetonate and triphenylphosphine is 1:1.75, carry out building-up reactions, and have CO bubble to produce.After question response does not have CO bubble to produce, stopped reaction, obtains the reaction solution containing acetylacetonatodicarrhodium rhodium.
Reaction solution is cooled to 5 DEG C, separates out yellow crystals.Filtration obtains yellow crystals, washs 3 times with the benzole solns of 5 DEG C, then 25 DEG C of vacuum-dryings, obtains finished product 86.51 grams.Determine that finished product is acetylacetonatodicarrhodium rhodium.
Carry out product analysis by the method for product analysis in embodiment 5, the results are shown in Table 1.
Embodiment 6
The present embodiment is for illustration of the method for olefin hydroformylation.
The rhodium dicarbonyl acetylacetonate 0.0249g that Example 1 prepares and 6.00g triphenylphosphine and 44.00g trimerization butyraldehyde are put into 100ml autoclave and are formed 50ml catalyst solution, pass into propylene, hydrogen and CO and carry out propene hydroformylation reaction in autoclave.Carrying out propene hydroformylation reaction condition is: temperature 100 DEG C, pressure 0.55MPa, propylene: H
2: CO=1:1:1(mol ratio), measure the initial catalyst speed of reaction of propene hydroformylation reaction.The results are shown in Table 2.
Embodiment 7
The present embodiment is for illustration of the method for olefin hydroformylation.
The rhodium dicarbonyl acetylacetonate 0.0249g that Example 2 prepares, measures the initial catalyst speed of reaction of propene hydroformylation reaction according to the condition of embodiment 6.The results are shown in Table 2.
Embodiment 8
The present embodiment is for illustration of the method for olefin hydroformylation.
The rhodium dicarbonyl acetylacetonate 0.0249g that Example 3 prepares, measures the initial catalyst speed of reaction of propene hydroformylation reaction according to the condition of embodiment 6.The results are shown in Table 2.
Embodiment 9
The present embodiment is for illustration of the method for olefin hydroformylation.
The acetylacetonatodicarrhodium rhodium 0.0477g that Example 5 prepares, measures the initial catalyst speed of reaction of propene hydroformylation reaction according to the condition of embodiment 6.The results are shown in Table 2.
Comparative example 3
Get the rhodium dicarbonyl acetylacetonate 0.0254g that comparative example 1 is synthesized, measure the initial catalyst speed of reaction of propene hydroformylation reaction according to the condition of embodiment 6.The results are shown in Table 2.
Comparative example 4
Get the acetylacetonatodicarrhodium rhodium 0.0477g that comparative example 2 prepares, measure the initial catalyst speed of reaction of propene hydroformylation reaction according to the condition of embodiment 6.The results are shown in Table 2.
Table 1
Table 2
Can be found out by the data of above-mentioned experimental result table 1, embodiment 1-4 is the preparation method adopting rhodium dicarbonyl acetylacetonate of the present invention, and the rhodium dicarbonyl acetylacetonate product obtained, has synthesis yield high, the feature that chloride ion content is low.As can be seen here, be rhodium precipitation by the converting feedstock of synthesis of acetyl acetone dicarbonyl rhodium in technical scheme provided by the invention, really can realize the present invention and reduce product chloride ion content, improve the goal of the invention of product synthesis yield.
Embodiment 5 is that the rhodium dicarbonyl acetylacetonate that embodiment 3 obtains is synthesized acetylacetonatodicarrhodium rhodium more further.Result data shows, the chloride ion content of the acetylacetonatodicarrhodium rhodium that method of the present invention obtains further is lower.And comparative example 1 and 2 adopts prior art preparation, the rhodium dicarbonyl acetylacetonate no matter prepared or the acetylacetonatodicarrhodium rhodium prepared, the chloride ion content of the product that the chloride ion content in product all obtains apparently higher than method of the present invention.
Embodiment 6-9 is that the product of embodiment 1-3 and 5 is for alkene formylation reaction.Under the condition identical in quality of the rhodium used, the chloride ion content not only in reaction system is low, and the initial catalyst speed of reaction of reaction is high, illustrates that the rhodium dicarbonyl acetylacetonate that preparation method of the present invention obtains has better catalytic activity.And preparation method of the present invention synthesizes the acetylacetonatodicarrhodium rhodium obtained further and also can have better catalytic activity.The chloride ion content of comparative example 3 and 4 then in reaction system is high, and the initial catalyst speed of reaction of reaction is low, poor catalytic activity.
As can be seen here; the chloride ion content of the rhodium dicarbonyl acetylacetonate product that method of the present invention obtains is low; meet industrial application requirement; rhodium dicarbonyl acetylacetonate need not be synthesized the catalytic activity that acetylacetonatodicarrhodium rhodium can have in hydroformylation of olefin; and method of the present invention obtains the content of rhodium in product and synthesis yield significantly improves, and is conducive to the utilization of Noble Metal Rhodium.
Embodiment 4 and the difference of embodiment 1 are control pH value in precipitin reaction different.As can be seen from experimental result, making the pH value of precipitin reaction be 7-8 is the preferred implementation obtaining preparation method's best effect of the present invention.
Claims (12)
1. a preparation method for rhodium dicarbonyl acetylacetonate, is characterized in that, the method comprises:
(1) under the condition of precipitin reaction, the Trichlororhodium aqueous solution is contacted with precipitation agent, to make rhodium element precipitate, obtain the precipitation containing rhodium element;
(2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm;
(3) under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, contact with methyl ethyl diketone after the described resolution of precipitate containing rhodium element that step (2) is obtained.
2. method according to claim 1, wherein, described precipitation agent is ammoniacal liquor and/or alkali metal hydroxide.
3. method according to claim 1 and 2, wherein, in the described Trichlororhodium aqueous solution, the volumetric molar concentration of rhodium is 0.1-5mol/L, and described precipitation agent is that the solution form of 0.1-5mol/L uses with volumetric molar concentration.
4. method according to claim 1, wherein, the condition of described precipitin reaction comprises: precipitation temperature is 5-10 DEG C; The consumption of precipitation agent makes the pH value after precipitin reaction between 7-10.
5. method according to claim 1, wherein, washing is lower than 500ppm to the chloride ion content in the described precipitation containing rhodium element.
6. method according to claim 5, wherein, described washing washing composition used is water or hexanaphthene, and wash temperature is 5-10 DEG C.
7. method according to claim 1, wherein, be dimethylformamide for dissolving the solvent of the described precipitation containing rhodium element, be equivalent to the rhodium element of 1 mole, the consumption of dimethylformamide is 1-3L.
8. method according to claim 1, wherein, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium comprises: the mol ratio of described methyl ethyl diketone and rhodium is 8-15:1; Temperature of reaction is 140-160 DEG C, and the reaction times is 50-90 minute.
9. according to the method in claim 1-2 and 4-8 described in any one, wherein, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium also comprises and carrying out in a nitrogen atmosphere.
10. method according to claim 3, wherein, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium also comprises carries out in a nitrogen atmosphere.
The method of 11. 1 kinds of olefin hydroformylations; the method comprises prepares rhodium dicarbonyl acetylacetonate; and obtained described rhodium dicarbonyl acetylacetonate is used for the hydroformylation reaction of alkene and synthetic gas; it is characterized in that, prepare the method for rhodium dicarbonyl acetylacetonate for the method in claim 1-10 described in any one.
12. methods according to claim 11, wherein, described hydroformylation of olefin is the reaction that propylene and synthetic gas generation hydroformylation reaction generate butyraldehyde-n and isobutyric aldehyde.
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| EP0505339A1 (en) * | 1991-03-20 | 1992-09-23 | Tanaka Kikinzoku Kogyo K.K. | Process of preparing rhodium nitrate solution |
| CN1769187A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Rhodium triiodid preparation method |
| CN102702270A (en) * | 2012-05-25 | 2012-10-03 | 杭州凯大催化金属材料有限公司 | Solvent-free synthesis method of acetylacetonatocarbonyltriphenylphosphine |
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| EP0505339A1 (en) * | 1991-03-20 | 1992-09-23 | Tanaka Kikinzoku Kogyo K.K. | Process of preparing rhodium nitrate solution |
| CN1769187A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Rhodium triiodid preparation method |
| CN102702270A (en) * | 2012-05-25 | 2012-10-03 | 杭州凯大催化金属材料有限公司 | Solvent-free synthesis method of acetylacetonatocarbonyltriphenylphosphine |
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